Method for enhancing the crop safety and efficacy of an agricultural chemical onto an agricultural substrate

ABSTRACT

A method for enhancing the crop safety and efficacy of an agricultural chemical onto an agricultural substrate comprising: applying to said agricultural substrate a sufficient amount of an adjuvant composition in the form of a spray mixture, wherein said adjuvant composition comprises: an oil a surfactant capable of increasing the spreading of water a surfactant capable of increasing the spreading of oil and optionally an agrochemical.

RELATED APPLICATIONS

This application claims benefit to Provisional Application Ser. No.60/705,674 filed Aug. 4, 2005 which is incorporated by reference in itsentirety for all useful purposes.

BACKGROUND OF THE INVENTION

It is well known that the use of spray adjuvants can enhance theefficacy of many pesticides and particularly herbicides. Spray adjuvantshave a wide array of functions which can improve spray application,enhance the efficacy of applied pesticides, or reduce off-target drift.ASTM E-1519 offers definitions of adjuvant terms and functions whichboth industry and academic researchers agree upon.

One such spray adjuvant consists of emulsifiable oils. Useful oils forthis practice include mineral oils, vegetable oils and alkylated fattyacids.

It is known that petroleum hydrocarbon spray oils increase the efficacyof herbicides, fungicides and other pesticides by enhancing thedeposition characteristics and wetting and spreading of the spraysolution resulting in a more even and uniform spray deposit or byincreasing the biological effect of certain pesticides. Other oils suchas once-refined vegetable oils are known to exhibit similar properties.Such spray oils can increase penetration and slow evaporation. Paraffinbased spray oil is a petroleum oil used as dormant spray, summer oil,carrier for pesticides or an adjuvant to increase the efficacy ofagricultural chemicals.

Other adjuvants designed to enhance the efficacy of pesticides are basedon emulsifiable alkylated fatty acids. More specifically, this group ofadjuvants contains methylated or ethylated fatty acids derived fromplant oils, such as soybean or rape seed oil. These adjuvants arecommonly referred to as methylated seed oil concentrates. They are wellknown for their ability to improve pesticide absorption through waxycuticles of plant surfaces, thus improving the uptake and effect ofherbicides.

A drawback of these oil adjuvants is their tendency to cause oraccentuate herbicide injury of desirable plants. It is generally agreedupon that if a herbicide has some tendency to cause phytotoxicity to aplant, that phytotoxicity will likely be enhanced with the addition ofan adjuvant. In some cases, this phytotoxic effect can be so severe thatpesticide labels warn against using oil-based spray adjuvants.

Another common spray adjuvant used to enhance herbicide efficacy isfertilizer. One example is urea-ammonium nitrate solutions (also knownas UAN or URAN solutions). UAN solutions are used to enhance theherbicidal effect of sulfonyl-urea (also known as SU) herbicides. Theaddition of UAN solutions to pesticide sprays has been reported toimprove the uptake of the pesticide into the plant. Spray depositscontaining UAN often retain moisture within the deposit, and thisimproves absorption. Another example of a fertilizer used as an adjuvantis ammonium sulfate (AMS). AMS has been well documented to increase theefficacy of herbicides.

Surfactants have also been widely used as spray adjuvants or componentsof pesticide formulations. When used as spray adjuvants, surfactants canenhance the efficacy of the applied pesticide.

A specific type of surfactant which has been found useful in theinvention is the polyether siloxanes. Polyether siloxanes are copolymersconsisting of polymethyl siloxanes and polyether. Depending on theirEO/PO ratio, the solubility of polyether siloxanes can be adjusted toobtain oil or water soluble products. Therefore polyether siloxanes arethe most versatile product group among the organomodified siloxanes.These siloxane surfactants can be used to enhance the spreading of wateror oil on agricultural substrates.

Emulsions are defined in the literature as either oil in water or waterin oil emulsions. The term oil in this case refers to any hydrophobicnon-water-soluble substance or mixture of substances. For the purposesof this invention, oil in water emulsions will be discussed. These arestable dispersions oil droplets in an aqueous medium.

A macro-emulsion contains oil droplets that are greater than 400 nm indiameter. These emulsions are characterized by a white opaque appearancedue to the scattering of light by the oil droplets. Mini-emulsionscontain oil droplets that are 100-400 nm in diameter. These emulsionsare characterized by a hazy, translucent appearance. Micro-emulsionscontain oil droplets that are 10-100 nm in diameter. The emulsions arecharacterized by a clear, transparent appearance. A full discussion ofemulsions and definitions can be found in Rosen's Surfactants andInterfacial Phenomena, 2^(nd) edition.

In agricultural chemical formulation, it is generally recognized thatformulations that form micro-emulsions are more effective at enhancingthe efficacy of the active pesticide. Micro-emulsion formulations arealso more phytotoxic than traditional macro-emulsion formulations.

It has well known how to produce micro-emulsions. and more particularly,how to produce micro-emulsions of methylated soybean oil. There alreadyexist on the market today, products which contain both methylatedsoybean oil and UAN fertilizer. These products are actuallymicro-emulsions of the methylated soybean oil into the UAN fertilizer.

One such product is Dyn-A-Pak, sold by Helena Chemical Company.Dyn-A-Pak contains methylated soybean oil, UAN fertilizer, surfactants,an organosilicone surfactant designed to enhance water spreading, and anorganosilicone surfactant designed to enhance oil spreading. Dyn-A-Pakhas been used to enhance the efficacy of imidazilone herbicides. Theproduct was introduced commercially in 1998 and was designed to deliverthe combination of UAN fertilizer and a methylated seed oil concentrate.The methylated seed oil is emulsified into the UAN fertilizer.Specifically, it was designed to enhance the efficacy of Pursuitherbicide. Pursuit herbicide is predominantly a soybean herbicide. Themarket for Pursuit was severely diminished by the advent of RoundupReady soybeans. Consequently, the market for Dyn-A-Pak was destroyed,since it was designed specifically for tank mixes with Pursuit.

SUMMARY OF THE INVENTION

Given what is known about oils, especially, micro-emulsified oils andphytotoxicity, it would be expected that this type adjuvant woulddramatically increase pesticide injury, especially in cases where thepesticide is already known to be phytotoxic to desirable foliage.Surprisingly, has been discovered that the unique combination ofsurfactants, nitrogen fertilizers, and micro-emulsified methylated fattyacids in Dyn-A-Pak actually decreases herbicide injury. Specifically,the use of both water and oil spreading organosilicone surfactantsprovide this unique combination of crop safety and herbicideenhancement. These adjuvants also enhance the desired herbicidal effecton undesirable weeds.

EXAMPLE 1

Ingredients % (w/w) UAN 32 58.5 Water 3.0 Methylated soybean oil 10.7AU-180 2.3 AU-940 0.2 Silicone defoamer 0.1 Amino ethyl ethanolamine 0.7Blend of surfactants for emulsification 24.5

In example 1, AU-180 is the organosilicone oil spreader. It is aPolyether siloxane copolymer surfactant. AU-940 is the organosiliconewater spreader. It is also a polyether siloxane copolymer surfactant.

The conventional alkylated vegetable oil formulation used for comparisonin field tests contain 90% by weight of methylated soybean oil and 10%nonylphenol ethoxylate.

The formulation of Example 1 has a pH of about 6.0 and is storage stableat temperatures from 4-45 degrees C. When applied to growing crops atthe rate of 0.5-1.0% v/v with imidazilone herbicides using water as thecarrier, the resulting weed control is superior to that of theimidazilone herbicide in water alone. Further, the injury to desirableplants is reduced in comparison with the addition of a standardalkylated vegetable oil concentrate and UAN fertilizer.

Examples of agrochemicals that can be used in the invention include butare not limited to pesticides, such as but not limited to a herbicide,an insecticide, a fungicide, a defoliant or blends thereof; a fertilizersuch as but not limited to a nitrogen containing fertilizer, a phosphatecontaining fertilizer, a potash containing fertilizer or blends thereof.

Examples of surfactants that could be used in this formulation includebut are not limited to:

Alcohol alkoxylates including but not limited to:

Based on branched and linear alcohols,

Those containing ethylene oxide or propylene oxide,

Alcohol alkoxylate sulfates,

Alkylphenol alkoxylates including but not limited to:

Nonylphenol and octylphenols.

Those containing ethylene oxide or propylene oxide

Alkanolamides,

Alkylaryl sulfonates,

Amine oxides,

Amines including but not limited to:

Fatty amine alkoxylates such as but not limited to tallowaminealkoxylates,

Betaine derivatives,

Block polymers of ethylene and propylene glycol,

Carboxylated alcohol or alkylphenol alkoxylates,

Diols, including but not limited to Butanediols,

Diphenyl sulfonate derivatives,

Ethers, including but not limited to

Butyl celluslove,

Butyl carbitol,

Ethoxylated amines,

Ethoxylated fatty acids,

Ethoxylated fatty esters and oils,

Ethoxylated triglycerides,

Fatty esters,

Glycerol esters,

Phosphate ester surfactants including but not limited to

Phosphate esters of alcohol alkoxylates,

Phosphate esters of alkylphenol alkoxylates,

Sarcosine derivatives,

Silicone-based surfactants,

Sorbitan derivatives including but not limited to:

Sorbitan esters,

Alkoxylated sorbitan esters,

Sucrose and glucose derivatives including but not limited to

Alkylpolyglucosides,

Sulfates and sulfonates of alkoxylated alkylphenols,

Sulfates of alcohols,

Tristyrylphenol Alkoxylates,

Other surfactants are disclosed in McCutcheon's Emulsifiers andDetergents, North American Edition, 2000.

Examples of oils that could be useful in this formulation include butare not limited to:

Alkylated fatty acid esters, include but are not limited to:

Methylated fatty acids, include but not limited to:

Methylated C6-C19 fatty acids,

Methylated Tall oil fatty acids,

Methylated Oleic acid,

Methylated Linoleic acid,

Methylated Linolenic acid,

Methylated Stearic acid,

Methylated Palmitic acid, and

blends thereof;

Ethylated fatty acids, include but are not limited to:

Ethylated C6-C19 fatty acids,

Ethylated Tall oil fatty acids,

Ethylated Oleic acid,

Ethylated Linoleic acid,

Ethylated Linolenic acid,

Ethylated Stearic acid,

Ethylated Palmitic acid, and

blends thereof;

Butylated fatty acids, include but are not limited to:

Butylated C6-C19 fatty acids,

Butylated Tall oil fatty acids,

Butylated Oleic acid,

Butylated Linoleic acid,

Butylated Linolenic acid,

Butylated Stearic acid,

Butylated Palmitic acid, and

blends thereof;

Alkylated natural oils, include but are not limited to:

Alkylated soybean oil, include but limited to:

Methylated soybean oil,

Ethylated soybean oil,

Butylated soybean oil, and blends thereof;

Alkylated canola oil, include but are not limited to:

Methylated canola oil,

Ethylated canola oil,

Butylated canola oil, and blends thereof;

Alkylated coconut oil, include but are not limited to:

Methylated coconut oil,

Ethylated coconut oil,

Butylated coconut oil, and blends thereof;

Alkylated sunflower oil, include but are not limited to:

Methylated sunflower oil,

Ethylated sunflower oil,

Butylated sunflower oil, and blend thereof;

Hydrocarbon oils include but are not limited to:

Mineral oils, including but are not limited to:

Paraffinic mineral oils,

Naphthenic mineral oils,

Aromatic mineral oils, and blends thereof;

Vegetable oils, include but are not limited to:

Soybean oil,

Canola oil,

Cottonseed oil, and blends thereof;

Fatty acids, include but are not limited to:

C6-C19 fatty acids,

Tall oil fatty acids,

Oleic acid,

Linoleic acid,

Linolenic acid,

Stearic acid,

Palmitic acid, and

blends thereof;

Polybutenes

Epoxified seed oils include but are not limited to:

Epoxified soybean oil and

Glycerides, including but not limited to

Glycerol

Other oils or oil substitutes.

Examples of the organosilicone surfactants useful in these formulationsare polyether-polymethylsiloxane-copolymers. These polyether siloxanesare copolymers consisting of polymethyl siloxanes and polyether.Depending on their EO/PO ratio, the solubility of polyether siloxanescan be adjusted to obtain oil or water soluble products. Thereforepolyether siloxanes are the most versatile product group among theorganomodified siloxanes. For the purposes of this invention, it ispreferred to use two separate organosilicone surfactants. One of theseorgano-silicone surfactant is characterized by it's ability to increasethe spreading ability of water on agricultural substrates. The other ofthese organosilicone surfactant is characterized by it's ability toincrease the spreading ability of oil droplets on agriculturalsubstrates. For both water or oil droplets, enhanced spreading isdetermined by ASTM E-2044.

Preferably the formulation contains at least one surfactant selectedfrom the group consisting of:

(a) fatty alkanolamides of the formula

wherein R is an alkyl group having from about 6 to about 25 carbonatoms; R and R″ are the same or different and are independently selectedfrom the group consisting of hydrogen,

—CH₂CH₂OH and

(b) PEG esters of the formula

wherein R² is C₂-C₂₅ fatty alkyl having from about 2 to about 25 carbonatoms, R³ is a fatty alkyl having from about 2 to about 25 carbon atomsor hydrogen and m is a number from 1 to about 100,

(c) silicone surfactants of the formula

wherein x is a number from 0 to about 5, y is a number from 1 to about5, a is a number from about 3 to about 25, b is a number from 0 to about25, n is a number from about 2 to about 4 and R⁶ is hydrogen, an alkylgroup having 1 to about 4 carbon atoms or an alkyl ester group having 1to about 4 carbon atoms,

(d) ethoxylated fatty acids of the formula

wherein R⁷ is an alkyl group having from about 6 to about 25 carbonatoms, p is a number from 1 to about 100,

(e) alkyl ethoxylates of the formulaR⁸O(CH₂CH₂O)_(q)H

wherein R⁸ is an alkyl group having from 1 to about 50 carbon atoms andq is a number from 1 to about 100,

(f) alkylphenol ethoxylates of the formula

wherein R⁹ is hydrogen or an alkyl having from about 1 to about 20carbons atoms, R¹⁰ is hydrogen or an alkyl having from about 1 to about20 carbon atoms and n is a number from 1 to about 100;

(g) polypropylene glycols of the formula

wherein t is a number from 1 to about 100,

wherein t is a number from 1 to about 100,

(h) amine ethoxylates of the formula

wherein g and h independently of one another are numbers from 1 to about100 and R″ is an alkyl having from 1 to about 25 carbon atoms and

(i) tristyrylphenol alkoxylate;

optionally a buffering agent in an amount sufficient to buffer pH belowabout 9 and higher than 2; and

optionally a fertilizer maybe present in the amount of 1.0% to 99%.

(j) fatty alcohols

saturated or unsaturated, branch or linear C8-C20 alcohols.

(k) fatty ethers

are those generally derived from fatty alcohols characterized by theformula ROR wherein R ia an alkyl group containing from 4 to 22 carbonatoms.

(l) alkoxylated glycerides

include those derived from glycerol and C6-22 fatty acid; glyceridesinclude glycerol mono/di-oleate.

The oil is preferably

i. vegetable oil,

ii. seed oil,

iii. paraffinic oil;

iv. fatty acids and blends thereof;

v. esterified fatty acids or blends thereof;

vi. saponified fatty acids or blends thereof;

vii. N,N-dimethylamide of the formulaRCON(CH₃)₂

wherein R is an alkyl chain derived from a fatty acid having about 6 toabout 18 carbon atoms; and

viii. polybutene or

ix. glyceride, including but not limited to glycerol.

The polybutenes are preferably of the formula

where n is a number from about 1 to about 50;

All the references described above are incorporated by reference in itsentirety for all useful purposes.

While there is shown and described certain specific structures embodyingthe invention, it will be manifest to those skilled in the art thatvarious modifications and rearrangements of the parts may be madewithout departing from the spirit and scope of the underlying inventiveconcept and that the same is not limited to the particular forms hereinshown and described.

1: A method for enhancing the crop safety and efficacy of anagricultural chemical onto an agricultural substrate comprising:applying to said agricultural substrate a sufficient amount of anadjuvant composition in the form of a spray mixture, wherein saidadjuvant composition comprises: an oil a surfactant capable ofincreasing the spreading of water a surfactant capable of increasing thespreading of oil and optionally, a fertilizer. an agrochemical, andoptionally, a fertilizer.
 2. The method as described in claim 1, whereinthe oil is vegetable oil, seed oil, paraffinic oil; fatty acids andblends thereof; esterified fatty acids or blends thereof; saponifiedfatty acids or blends thereof; N,N-dimethylamide of the formulaRCON(CH₃)₂ wherein R is an alkyl chain derived from a fatty acid havingabout 6 to about 18 carbon atoms; polybutene or glyceride.
 3. The methodas described in claim 1, wherein the adjuvant composition contains atleast one surfactant selected from the group consisting of: fattyalkanolamides of the formula

 wherein R is an alkyl group having from about 6 to about 25 carbonatoms; R and R″ are the same or different and are independently selectedfrom the group consisting of hydrogen, —CH₂ CH₂OH and

(b) PEG esters of the formula

 wherein R² is C₂-C₂₅ fatty alkyl having from about 2 to about 25 carbonatoms, R³ is a fatty alkyl having from about 2 to about 25 carbon atomsor hydrogen and m is a number from 1 to about 100; (c) siliconesurfactants of the formula

 wherein x is a number from 0 to about 5, y is a number from 1 to about5, a is a number from about 3 to about 25, b is a number from 0 to about25, n is a number from about 2 to about 4 and R⁶ is hydrogen, an alkylgroup having 1 to about 4 carbon atoms or an alkyl ester group having 1to about 4 carbon atoms; (d) ethoxylated fatty acids of the formula

 wherein R⁷ is an alkyl group having from about 6 to about 25 carbonatoms, p is a number from 1 to about 100; (e) alkyl ethoxylates of theformulaR⁸O(CH₂CH₂O)_(q)H  wherein R⁸ is an alkyl group having from 1 to about50 carbon atoms and q is a number from 1 to about 100; (f) alkylphenolethoxylates of the formula

 wherein R⁹ is hydrogen or an alkyl having from about 1 to about 20carbons atoms, R¹⁰ is hydrogen or an alkyl having from about 1 to about20 carbon atoms and n is a number from 1 to about 100; (g) polypropyleneglycols of the formula

 wherein t is a number from 1 to about 100; (h) amine ethoxylates of theformula

 wherein g and h independently of one another are numbers from 1 toabout 100 and R¹¹ is an alkyl having from 1 to about 25 carbon atoms;(i) tristyrylphenol alkoxylate; optionally a buffering agent in anamount sufficient to buffer pH below about 9 and higher than 2; andoptionally a fertilizer maybe present in the amount of 1.0% to 99%; (j)fatty alcohols which are saturated or unsaturated, branch or linearC8-C20 alcohols. (k) fatty ethers which are those generally derived fromfatty alcohols characterized by the formula ROR wherein each Rindependently is an alkyl group containing from 4 to 22 carbon atoms and(l) glycerides.
 4. The method as described in claim 1, wherein thefertilizer is a nitrogen containing fertilizer, a phosphate containingfertilizer, a potash containing fertilizer or blends thereof.
 5. Themethod as described in claim 1, wherein the water spreading surfactantis an organosilicone surfactant.
 6. The method as described in claim 1,wherein the oil spreading surfactant is an organosilicone surfactant. 7.The method as described in claim 5, wherein the organosiliconesurfactant is a polyether-polymethylsiloxane copolymer.
 8. The method asdescribed in claim 6, wherein the organosilicone surfactant is apolyether-polymethylsiloxane copolymer.
 9. The method as described inclaim 1, wherein the agrochemical is a pesticide.
 10. The method asdescribed in claim 9, wherein the pesticide is a herbicide, aninsecticide, a fungicide, a defoliant or blends thereof
 11. A method fortreating an agricultural substrate comprising: contacting said substratewith an agrochemical composition comprising a agrochemical and aadjuvant comprising: an oil; a surfactant capable of increasing thespreading of water; a surfactant capable of increasing the spreading ofoil; optionally fertilizer; and water by spraying said composition ontosaid substrate using common agrochemical practices with the proviso thatthe spray mixture provides both crop safety and enhanced efficacy of theagrochemical.
 12. The method as described in claim 11, wherein the oilis vegetable oil; seed oil; paraffinic oil; fatty acids and blendsthereof; esterified fatty acids or blends thereof; saponified fattyacids or blends thereof; N,N-dimethylamide of the formulaRCON(CH₃)₂ wherein R is an alkyl chain derived from a fatty acid havingabout 6 to about 18 carbon atoms; polybutene or glyceride.
 13. Themethod as described in claim 11, wherein the adjuvant compositioncontains at least one surfactant selected from the group consisting of:fatty alkanolamides of the formula

 wherein R is an alkyl group having from about 6 to about 25 carbonatoms; R and R″ are the same or different and are independently selectedfrom the group consisting of hydrogen, —CH₂ CH₂OH and

(b) PEG esters of the formula

 wherein R² is C₂-C₂₅ fatty alkyl having from about 2 to about 25 carbonatoms, R³ is a fatty alkyl having from about 2 to about 25 carbon atomsor hydrogen and m is a number from 1 to about 100; (c) siliconesurfactants of the formula

 wherein x is a number from 0 to about 5, y is a number from 1 to about5, a is a number from about 3 to about 25, b is a number from 0 to about25, n is a number from about 2 to about 4 and R⁶ is hydrogen, an alkylgroup having 1 to about 4 carbon atoms or an alkyl ester group having 1to about 4 carbon atoms; (d) ethoxylated fatty acids of the formula

 wherein R⁷ is an alkyl group having from about 6 to about 25 carbonatoms, p is a number from 1 to about 100; (e) alkyl ethoxylates of theformulaR⁸O(CH₂CH₂O)_(q)H  wherein R⁸ is an alkyl group having from 1 to about50 carbon atoms and q is a number from 1 to about 100; (f) alkylphenolethoxylates of the formula

 wherein R⁹ is hydrogen or an alkyl having from about 1 to about 20carbons atoms, R¹⁰ is hydrogen or an alkyl having from about 1 to about20 carbon atoms and n is a number from 1 to about 100; (g) polypropyleneglycols of the formula

 wherein t is a number from 1 to about 100; (h) amine ethoxylates of theformula

 wherein g and h independently of one another are numbers from 1 toabout 100 and R¹¹ is an alkyl having from 1 to about 25 carbon atoms;(i) tristyrylphenol alkoxylate; optionally a buffering agent in anamount sufficient to buffer pH below about 9 and higher than 2; andoptionally a fertilizer maybe present in the amount of 1.0% to 99%; (j)fatty alcohols which are saturated or unsaturated, branch or linearC8-C20 alcohols; (k) fatty ethers which are those generally derived fromfatty alcohols characterized by the formula ROR wherein each Rindependently is an alkyl group containing from 4 to 22 carbon atoms and(l) glycerides.
 14. The method as described in claim 11, wherein thefertilizer is a nitrogen containing fertilizer, a phosphate containingfertilizer, a potash containing fertilizer or blends thereof.
 15. Themethod as described in claim 11, wherein the water spreading surfactantis an organosilicone surfactant.
 16. The method as described in claim11, wherein the oil spreading surfactant is an organosiliconesurfactant.
 17. The method as described in claim 15, wherein theorganosilicone surfactant is a polyether-polymethylsiloxane copolymer.18. The method as described in claim 16, wherein the organosiliconesurfactant is a polyether-polymethylsiloxane copolymer.
 19. The methodas described in claim 11, wherein the agrochemical is a pesticide. 20.The method as described in claim 19, wherein the pesticide is aherbicide, an insecticide, a fungicide, a defoliant or blends thereof.21. The method according to claim 1, wherein the adjuvant is present inthe amount of 0.0001 to 10% by weight of said spray mixture.
 22. Themethod according to claim 1, wherein the pH of the spray mixture is from2 to
 7. 23. The method according to claim 1, wherein a fertilizer ispresent in the amount of 0.0001 to 99% by weight.
 24. A method fortreating an agricultural substrate in the form of vegetation or soilcomprising: providing an agrochemical composition in the form of a spraymixture containing surfactants, fertilizer, a surfactant capable ofincreasing the spreading of water, a surfactant capable of increasingthe spreading of oil and an agrochemical, water, and at least one of avegetable oil, modified vegetable oil, modified oil, natural oil or aparaffin oil, applying said agrochemical composition to said substrateby spraying a sufficient amount of said composition onto said substrateby convectional agrochemical practices and B) reducing the phytoxicresponse of a pesticide.
 25. The method according to claim 1 whereinsaid spray mixture further contains a defoamer.
 26. The method accordingto claim 1, wherein said spray mixture further contains an agent in anamount sufficient to lower the pH of the spray solution to below
 7. 27.The method according to claim 11, wherein said spray mixture furthercontains a defoamer.
 28. The method according to claim 11, wherein saidspray mixture further contains an agent in an amount sufficient to lowerthe pH of the spray solution to below
 7. 29. The method as described inclaim 1 wherein the adjuvant concentrate composition comprises at leastone water soluble Polyether-polymethylsiloxane-copolymer and/or oilsoluble Polyether-polymethylsiloxane-copolymer, and at least one memberselected from the group consisting of: vegetable oil; seed oil;paraffinic oil; fatty acids and blends thereof; esterified fatty acidsor blends thereof; saponified fatty acids or blends thereof;N,N-dimethylamide of the formulaRCON(CH₃)₂ wherein R is an alkyl chain derived from a fatty acid havingabout 6 to about 18 carbon atoms; polybutenes of the following formula

where n is a number from about 1 to about 50; glyceride, and/or at leastone surfactant selected from the group consisting of fatty alkanolamidesof the formula

 wherein R is an alkyl group having from about 6 to about 25 carbonatoms; R and R″ are the same or different and are independently selectedfrom the group consisting of hydrogen, —CH₂ CH₂OH and

(b) PEG esters of the formula

 wherein R² is C₂-C₂₅ fatty alkyl having from about 2 to about 25 carbonatoms, R³ is a fatty alkyl having from about 2 to about 25 carbon atomsor hydrogen and m is a number from 1 to about 100; (c) siliconesurfactants of the formula

 wherein x is a number from 0 to about 5, y is a number from 1 to about5, a is a number from about 3 to about 25, b is a number from 0 to about25, n is a number from about 2 to about 4 and R⁶ is hydrogen, an alkylgroup having 1 to about 4 carbon atoms or an alkyl ester group having 1to about 4 carbon atoms; (d) ethoxylated fatty acids of the formula

 wherein R⁷ is an alkyl group having from about 6 to about 25 carbonatoms, p is a number from 1 to about 100; (e) alkyl ethoxylates of theformulaR⁸O(CH₂CH₂O)_(q)H  wherein R⁸ is an alkyl group having from 1 to about50 carbon atoms and q is a number from 1 to about 100; (f) alkylphenolethoxylates of the formula

 wherein R⁹ is hydrogen or an alkyl having from about 1 to about 20carbons atoms, R¹⁰ is hydrogen or an alkyl having from about 1 to about20 carbon atoms and n is a number from 1 to about 100; (g) polypropyleneglycols of the formula

 wherein t is a number from 1 to about 100; (h) amine ethoxylates of theformula

 wherein g and h independently of one another are numbers from 1 toabout 100 and R¹¹ is an alkyl having from 1 to about 25 carbon atoms;(i) tristyrylphenol alkoxylate; optionally a buffering agent in anamount sufficient to buffer pH below about 9 and higher than 2; andoptionally a fertilizer maybe present in the amount of 1.0% to 99%; (j)fatty alcohol which is saturated or unsaturated, branch or linear C8-C20alcohols; (k) fatty ether which is derived from fatty alcoholscharacterized by the formula ROR wherein R ia an alkyl group containingfrom 4 to 22 carbon atoms. (l) glyceride and/or optionally an agent inan amount sufficient to buffer pH below 8; and optionally a fertilizermaybe present in the amount of 1.0% to 99%.
 30. The method as describedin claim 26, wherein the pH modifying agent is selected from the groupconsisting of alkylaryl polyethoxy phosphate ester, C₁-C₆ carboxylicacid, C₁-C₆ dicarboxylic acid, phosphoric acid, citric acid, glutaricacid, gluconic acid, lactic acid, glycolic acid, acrylic acid, andcarboxylated alcohol ethoxylate.
 31. A composition which comprises: Anoil Surfactants Fertilizer An agrochemical Optionally, a surfactantcapable of increasing the spreading of water And optionally, asurfactant capable of increasing the spreading of oil herein saidcomposition may be added to an agriculturally acceptable diluent andapplied to an agriculturally acceptable substrate.
 32. The compositionas described in claim 31, wherein the oil is vegetable oil; seed oil;paraffinic oil; fatty acids and blends thereof; esterified fatty acidsor blends thereof; saponified fatty acids or blends thereof;N,N-dimethylamide of the formulaRCON(CH₃)₂ wherein R is an alkyl chain derived from a fatty acid havingabout 6 to about 18 carbon atoms; polybutene or glyceride.
 33. Thecomposition as described in claim 31, wherein the adjuvant compositioncontains at least one surfactant selected from the group consisting of:fatty alkanolamides of the formula

 wherein R is an alkyl group having from about 6 to about 25 carbonatoms; R and R″ are the same or different and are independently selectedfrom the group consisting of hydrogen, —CH₂CH₂OH and

(b) PEG esters of the formula

 wherein R² is C₂-C₂₅ fatty alkyl having from about 2 to about 25 carbonatoms, R³ is a fatty alkyl having from about 2 to about 25 carbon atomsor hydrogen and m is a number from 1 to about 100; (c) siliconesurfactants of the formula

 wherein x is a number from 0 to about 5, y is a number from 1 to about5, a is a number from about 3 to about 25, b is a number from 0 to about25, n is a number from about 2 to about 4 and R⁶ is hydrogen, an alkylgroup having 1 to about 4 carbon atoms or an alkyl ester group having 1to about 4 carbon atoms; (d) ethoxylated fatty acids of the formula

 wherein R⁷ is an alkyl group having from about 6 to about 25 carbonatoms, p is a number from 1 to about 100; (e) alkyl ethoxylates of theformulaR⁸O(CH₂CH₂O)_(q)H  wherein R⁸ is an alkyl group having from 1 to about50 carbon atoms and q is a number from 1 to about 100; (f) alkylphenolethoxylates of the formula

 wherein R⁹ is hydrogen or an alkyl having from about 1 to about 20carbons atoms, R¹⁰ is hydrogen or an alkyl having from about 1 to about20 carbon atoms and n is a number from 1 to about 100; (g) polypropyleneglycols of the formula

 wherein t is a number from 1 to about 100; (h) amine ethoxylates of theformula

 wherein g and h independently of one another are numbers from 1 toabout 100 and R¹¹ is an alkyl having from 1 to about 25 carbon atoms;(i) tristyrylphenol alkoxylate optionally a buffering agent in an amountsufficient to buffer pH below about 9 and higher than 2; and optionallya fertilizer maybe be present in the amount of 1.0% to 99%; (j) fattyalcohol which is saturated or unsaturated, branch or linear C8-C20alcohols; (k) fatty ether which is derived from fatty alcoholscharacterized by the formula ROR wherein R ia an alkyl group containingfrom 4 to 22 carbon atoms and (l) glyceride.
 34. The composition asdescribed in claim 31, wherein the fertilizer is selected from thegroup: a nitrogen containing fertilizer; a phosphate containingfertilizer; a potash containing fertilizer or blends thereof.
 35. Thecomposition as described in claim 31, wherein the water spreadingsurfactant is an organosilicone surfactant.
 36. The composition asdescribed in claim 31, wherein the oil spreading surfactant is anorganosilicone surfactant.
 37. The composition as described in claim 35,wherein the organosilicone surfactant is a polyether-polymethylsiloxanecopolymer.
 38. The composition as described in claim 36, wherein theorganosilicone surfactant is a polyether-polymethylsiloxane copolymer.39. The composition as described in claim 31, wherein the agrochemicalis a pesticide.
 40. The method as described in claim 39, wherein thepesticide is selected from the group: Herbicide; Insecticide; Fungicide;Defoliant and blends thereof.
 41. The method according to claim 1, toreduce the damage caused by an agrochemical with a balanced, storagestable, spray mixture and/or adjuvant composition that will not causeunwanted damage to a desired plant or crop.